Water-insoluble azo dyestuffs



Patented Dec. 29, 1942 r ()FFICE WATER-INSOLUBLE AZO DYESTUFFS Werner Zerweck, Josef Riedmair, and Walter Brunner, Frankfort- Germany, assignors t Corporation, New York Del No Drawing.

4: Claims.

Our present invention relates to waterinsoluble azodyestuffs more particularly to those of the general formula:

aware wherein the Rs stand for radicles of the benzene series and X for a member of the group consisting of hydrogen, halogen, alkyl, alkoxy and aryloxy groups of the benzene series.

The present new azodyestufis are special embodiments of the group of waterinsoluble azodyestuffs described and claimed in U. S. Patent No. 2,030,327. They are obtained by combining in substance or on a substratum the diazocompounds of amino arylethers of the benzene series with acetoacetylaminoebeenzothiazole compounds containing in the 6-position of the benzthiazole radicle an aryloxy group of the benzene series.

The dyestufis produced in substance are generally yellowish substances, suitable for preparing valuable color lakes, while those produced on the fiber, especially the cellulosic fiber, according to one of the usual dyeing or printing processes, generally yield yellow to reddish yellow to greenish yellow shades of good fastness properties. They are distinguished within the scope of U. S. Patent 2,030,327 by a particular brightness and strength of shades to such a degree as hitherto unknown for waterinsoluble yellow azodyestufis.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in degrees centigrade.

Example 1 8.9 parts of 2-acetoacetylamino-5-methoxy-6- phenoxyb'enzthiazol are mixed with about 20 parts of alcohol and dissolved in 25.:parts of a caustic soda solution of 4% strength and 300 parts of water. Then while well stirring dilute acetic acid is dropped in until a slightly acid reaction, whereby the acetoacetyl compound separates in a finely divided form. After the addition of 70 parts of a dilute sodium acetate solution of 25% strength and 80 parts of technical pyridine at about 0 to 5 a diazosolution is slowly added, which has been prepared in the usual manner from 6.2

n-the-Main-Fechenheim,

0 General Aniline & Film N.-Y., a corporation of Application January 7, 1941, Serial In Germany January 24, 1940 parts of 2-amino-4.6-dimethyl-5-chlorodiphenylether. The formed azodyestufi of the formula:

1 gr. of 2-acetoacetylamino-5-methoxy-6- phenoxy-benzthiazol is dissolved in one liter of water with the addition of 3 ccms. of alcohol and 0.5 com. of a caustic soda solution of 38 B. 5O grs. of cotton yarn are impregnated with such a solution with the addition of sodium sulfate at about 30 and developed with a solution containing 1.5 grs. of diazotized 2-amino'-4.l'-dichlorodiphenylether and an excess of sodium acetate, well rinsed and soaped. In this manner on the fiber the dye's'tuff of the formula:

is produced, dyeing very clear and strong yellow shades of very good fastness properties.

Example 3 rodiphenylether with the sodium salt of the methylamino-acetic acid are dissolved with the addition of 50 parts of di-(oxethyl) -su1fide in 300 parts of a caustic soda solution of 38 B. and 320 yielding when produced in substance valuable bright greenish yellow color lakes and when produced on the fiber bright greenish yellow shades of good fastness properties.

parts of water. This solution is converted by mix- 2. The water insoluble azodyestufi of the ing it with 500 parts of a neutral starch-tragaformula: canth thickening into a paste form which is suitable for printing textile good, the tissue is printed 1130 O- therewith and the dyestufi of the formula: 10 HCO J C N O N s 1H: C-NHCO7CH -COCHa O O N 01- 0 Cl Jul \ yielding when produced in substance valuable clear and strong yellow color lakes and when HJC- 0 produced on the fiber clear and strong yellow shades of good fastness properties. 01 H3 3 Th wat r ins lubl zod tuff f th is developed in the usual manner by steaming in e o e a yes 0 e an acetic-formic-acid atmosphere. In this man- N ner bright greenish yellow prints of good fastness properties are obtained.

C-NH-CO-CH-DO-CH. A similar result is obtained when using the O equivalent amount of 2-acetoacetylamino-5- 5 s methoxy-S-phenoxy-benzthiazol as coupling com- N ponent.

In the following table these and some further H;C- 0-D dyestufis produced according to our present in- I vention are named: 01 H,

Combining component Diem-component Shade 2-acetoacetylamino-S-rneth- 2-zin1ino-4-ch1orodiphenylether Clear strong yellow. oxy-li-phenoxybenzthiazol.

Do 2-arnino-4.G dirnethyl-5-chlorodiphenylether Very bright greenish yellow.

4-amino-Z-chloro-5-methyl-diphenylether Clear yellow. 4-amino-2.4'-dichloro-5-rnethyldiphenylether. Do. 4-ainino-2-chloro-3-rnethoxydiphenylether Do. 4-amino-2.4'-dichloro-3-methoxydiphenylether Do.

Do 4'8mlI10'2.5-dlfllethyl-dlphellylethel Strong greenish yellow.

2-acctoacetylamino-G-phen- 2-amino4.4- liehloro-diphenylether Strong clear yellow.

oxybenzthiazol.

D0 2-amino-4-ehloro-diphenylether Do.

Do- 2-amino-4.6-dirnethyl-5-chlorodiphenylether Very bright greenish yellow.

Do.- 4-amino-2-chloro-fi-rnethyldiphenylether Clear greenish yellow.

Do-. 4-amino-2.4'-dichloro-5-methyl-diphenylether. Strong yellow.

Do-. 4-amino 2-ehloro-3-methoxy-diphenyl-ether Very bright greenish yellow.

D0. 4-arnino-2.4-dichloro-3-methoxy-diphenyl-ether Do.

Do 4-amino-2.5-dimethyldiphenylether Clear reddish yellow.

2- ecetoacetylami m 2-amino-4-ch1oro-diphenylether Clear yellow.

oxy-6-o-chloro-phenoxybenzthiazol.

Do 2-amino4.4-di-chloro-diphenylether Clear reddish yellow. Do 2-amino-4.6-dimethy1-5-chloro-diphenylether.-- Brilliant greenish yellow. 2 ecetoacetylamlno 2-amino-4-chloro-diphenylether Clear strong yellow.

oxy 6 m chloro phonoxy benzthlazol Z-amino-Lfl-di-chloro-diphenylether Do. 2-an1ino-4.fi-dlrnethyl-5-chloro-diphenylether. Clear greenish yellow. 2-ainino-4-ehlorodi-phcnylether Strong yellow. nxy-fi-p-chloro-phenoxybenzthiazol.

Do 2-arnino-4.4-dichloro-diphenylether Do. 2-acetoacetylamino-6-o-ehloro- Z-aminolddimethyl-S-chlorodiphenyl-eth Brilliant greenish yellow.

phenoxy-benzthiazol. 2-acetoaeetylaniindismehloro- ,do Do.

phenoxy-benzthiazol. 2-acetoaeety1amino-6-p-chloro- Do.

phenoxy-benzthiazol. 2-acetoacetylarnino-5-cl1loro-6- 2-amino-4-chloro-diphenylether Do.

phenoxy-benzthiazol. I Z-acetoacetylamino-5-methyl- .do Clear reddish yellow.

fi-phenoxy-benzthiazol. 2-acetoacety1amino-5.fi-di- 2-amino-4.6-dimethyl-5chlor0-di-pl1enyl-ctbe1 Greenish yellow.

phenoxybenzthiazol.

We claim: yielding when produced in substance valuable 1. The water insoluble azodyestuff of the ht greenish y w color lakes and when P formula: duced on the fiber bright greenish yellow shades of good fastness properties.

4. Water-insoluble azo dyestuffs of the general formula:

N Y O /C--NHCO-CI;HCOCHS O O s i I Cl X wherein Y is selected from the class consisting and of hydrogen and methoxy and X is selected from the class consisting of H|C 0Q & the bond in the latter radicles designating their point of attachment to the azo group. Cl CH:

WERNER ZERWECK. J OSEF RIEDMAIR. WALTER BRUNNER. 

